It is widely appreciated that single-molecule spectroscopy (SMS) can be used to measure properties of individual molecules which would normally be obscured in an ensemble-averaged measurement. In this article, we show how SMS can be used to investigate intramolecular electron transfer (IET) processes in model dimer systems composed of two perylene chromophores connected via an adjustable bridge. The fluorescence behaviors of a large number of molecules are cataloged and the results statistically analyzed to gauge information about the range of behaviors of the ensemble. Single-molecule fluorescence time trajectories reveal “blinks”, momentary losses in fluorescence (>20 ms to seconds in duration), which are attributed to discrete IET excursions to the charge-separated (CS) state. We find that fluorescence blinking behavior is dependent on bridge length and chromophore geometry, which affect the electronic coupling and therefore the IET. The statistical trends observed in this analysis are used to corroborate the assignment of the blinking behavior to IET. These results and methodology have implications for molecular electronics, where understanding and controlling the range of possible behaviors inherent to molecular systems will likely be as important as understanding the individual behavior of any given molecule.

Donor-acceptor nanofibril composites have been fabricated, and the dependence of their photocurrent response on the structure and morphology of the donor part has been systematically investigated. The nanofibril composites were composed of template nanofibers, assembled from an electron acceptor molecule, perylene tetracarboxylic diimide (PTCDI), onto which (through drop-casting) various electron donor molecules (D1-D4) were coated. The donor molecules have the same π-conjugated core, but different side groups. Due to the different side groups, the four donor molecules showed distinctly different propensity for intermolecular aggregation, with D1-D3 forming segregated phases, while D4 prefers homogeneous molecular distribution within the film. It was found that the nanofibril composites with D4 exhibit the highest photocurrent, whereas those with aggregation-prone D1-D3 exhibited much lower photocurrent under the same illumination condition. Solvent annealing is found to further enhance the aggregation of D1-D3 but facilitate more uniform molecular distribution of D4 molecules. As a result, the photocurrent response of PTCDI fibers coated with D1-D3 decreased after vapor annealing, whereas those coated with D4 further increased. The detrimental effect of the aggregation of donor molecules on the PTCDI fiber is likely due to the enhanced local electrical field built up by the high charge density around the aggregate-nanofiber interface, which hinders the charge separation of the photogenerated electron-hole pair. The results reported in this study give further insight into the molecular structural effect on photoconductivity of hybrid materials, particularly those based on donor-acceptor composites or interfaces, and provide new molecular design rules and material processing guidelines to achieve high photoconductivity.

Perylene tetracarboxylic diimide (PTCDI) derivatives have been extensively investigated for one-dimensional (1D) self-assembly and their applications in optoelectronic devices. Our study on self-assembled PTCDI nanofiber materials revealed a persistent photoconductivity (PPC) effect, which is sustained conductivity after illumination is terminated. A comprehensive understanding of the PPC effect in PTCDI nanofibril materials will enable us to explore and enhance their optoelectronic applications. Here, we have investigated the PPC effect in the nanofibers assembled from 1-methylpiperidine-substituted perylene tetracarboxylic diimide (MP-PTCDI) with respect to the PPC relaxation at different temperatures, illumination power densities, molar amount, and morphology of the PTCDI film deposited on the interdigitated electrodes. The photocurrent relaxation was also performed on several other PTCDI nanofiber materials for comparative study. We conclude that the significant PPC effect in MP-PTCDI nanofibers can be attributed to the electrical potential fluctuations caused by the structure defects, which thus hinder the recombination of charge carriers. This study may provide new design rules for fabrication of molecular semiconductor materials with strong PPC in order to approach high efficiency of photovoltaics and photocatalysis.